LT3079B - Flour polymer absorbency liquids and blood by pressing it, process for the production and use thereof in textiles for use body hygiene - Google Patents

Abstract

PCT No. PCT/EP93/03586 Sec. 371 Date Jun. 30, 1995 Sec. 102(e) Date Jun. 30, 1995 PCT Filed Dec. 17, 1993 PCT Pub. No. WO94/15651 PCT Pub. Date Jun. 21, 1994The invention relates to powdery cross-linked polymers (superabsorbers) capable of absorbing aqueous liquids and blood, which are formed of 55-99.9%-wt. polymerized unsaturated, polymerizable acid-groups-comprising monomers which are neutralized to the extent of at least 25 mol-%, b) 0-40%-wt. polymerized unsaturated monomers copolymerizable with a), c) 0.1-5.0%-wt. of a cross-linking agent, d) 0-30%-wt. of a water-soluble polymer, whereby the weight amounts of a) to d) relate to anhydrous polymers, characterized in that 100 parts of the particle-shaped polymers have been mixed with an aqueous solution consisting of a maximum of 10 parts of an at least 10% phosphoric acid and a) 0.05-0.3 parts of a compound capable of reacting with at least two carboxyl groups and not comprising an alkali-salt-forming group in the molecule, and/or b) 0.05-1 parts of a compound capable of reacting with at least two carboxyl groups and comprising an alkali-salt-forming group in the molecule, and that they have been heated to 150 DEG -250 DEG C. The superabsorbers according to the invention have a high retention capacity, high gel strength and a high absorption under load and can be manufactured without an organic solvent and with only a small amount of treatment agent for the surface treatment of the powdery polymer. The invention further relates to the use of said polymers in textile constructions for the absorption of body liquids, said constructions preferably consisting of 2 to 80%-wt. superabsorber and the remainder up to 100 of hydrophilic fibers.

Description

The present invention relates to a powder :, / having /: spatially structured polymers (superabsorbents)> / absorbing aqueous fluids and blood having improved properties in terms of swelling and aqueous loading capacity; method of obtaining these / polymers: and their use in sanitary ware, such as baby //(=/:./ diapers, and also / women's / ;: hygiene and cases.

/.Superabsorbents: Yes.

spatial structure, polymers that can absorb large quantities of 15 aqueous fluids and human body fluids such as urine and blood by swelling and forming / hydrogels and, under certain pressures, retain those fluids. Thanks to these characteristic absorption properties, polymers are mainly used in the preparation of sanitary / infant products, such as baby diapers 20 and female taihpons.

At present (in the case of commercially available superabsorbents, we are talking about:) spatial / structured polyacrylic acids or volumetric copolymers of starch-acrylic acid in which the carboxylic groups are partially neutralized with sodium hydroxide or potassium alkali. are obtained, essentially, by two methods.

According to the first method ',. in aqueous. in the solution, the partially neutralized acrylic acid is, in the presence of a multifunctional compound forming a transverse / linkage / radical, the result of polymerization, transferred to (gel / which may be crushed, / dried, ground and sieved to a desired particle size). or intermittently Typical methods of production are described, for example, in US

7? ^ 7) / - // - 7-72 '7No. 42,86082, DE no to 2706135 5 r US no. 4076663 in Patent Specifications (PA). - m //.) ·. · / The second method is inverse. suspension and 5 'emulsion polymerization method. In this process, an aqueous solution of partially neutralized acrylic acid is dispersed in a hydrophotic, organic solvent, using radical colloids or emulsifiers, and polymerization is initiated using radical initiators. Upon completion of the polymerization, the Trs reaction mixture is thoroughly mixed with water and the polymer product is filtered off and dried to form a cross-linking reaction by introducing a multifunctional component into the polymer; a crosslinking compound which is dissolved in the monomer solution and / or during the manufacturing step by reaction with a suitable crosslinking compound with polymer functional groups. The principle of the production method is described in Example 7. OS Kr. 4340706 / DE

No: 3713601 and DE no. 2840Ό10 in the descriptions of the patents (PA).

In the development of superabsorbents, the first consideration was given to their ability to swell significantly in contact with the liquid, also known as the "full swelling capacity";

however, this later appeared to depend only on the amount of fluid absorbed, but also on the strength of the swollen gel. The absorptive capacity, the ability to swell, or the so-called free swelling capacity, on the one hand, and having. The spatial structure of the polymer gel, on the other hand, reflects the opposite properties / as is already known from US PA 73247141 and later from US 'PA Re 32649. This means that polymers with extremely high absorbency have only a minor property. swelling of the gel., which causes the gel to deform and impede further fluid distribution and absorption after application of pressure (eg body pressure). Therefore, according to US PA Re .32649 diaper * toT 3079 B, 0. 0 / // '0 000- 30 // /, 0, 0 /. / 0 / - 0 0 0/0 / the structure must have a harmonious ratio of the following types of superabsorbene to provide fluid absorption, fluid transport, diaper and skin dryness. At the same time, this does not only depend on the to retain the fluid and then. again initially free to swell but .and from that polymer.

0 / can absorb liquids also under · simultaneous counter-pressure, i.e. when absorbing fluid, as is the case under practical circumstances, · when a baby or 0 person is sitting or lying on a sanitary article, or when, for example, cutting forces occur when the feet are moved. The specific absorbent property of EPi 0339461 is defined as absorption under pressure.

^15th

For understandable aesthetic reasons and for environmental reasons (waste / volume reduction), the increasing tendency to · produce smaller and smaller sanitary ware can only be accomplished by reducing the amount of bulky fluff in the diaper while increasing the amount of superabsorbent. Thus, the superabsorbents have to take on additional fluid absorption and transport

/.•-./.'.Functions previously performed by fluff.

If hygiene products such as. In diapers, the amount of superabsorbent is increased to 40% or even 60% and more, and commercially available superabsorbents become virtually unused. The absorption of the fluid, especially under pressure, becomes too slow. The particles tend to form a coagulated gel. ' The resulting gel barriers block further fluid transport. This phenomenon is known as gel blocking.

To produce superabsorbent polymers with a unique combination of properties such as high retention capacity, high gel

) ./ .. 7'7'7 / 7) · 4:

) strength and high ability to absorb under pressure, powdered polymers need further processing.

According to GB 2119384A, polymers are treated with compounds having at least two functional groups which can react in the form of particles in the surface layer.

'polymer carboxylic' groups, significant improvement in properties is achieved.

, DE OS 35 23 '617. discloses a method of further treating a powdered polymer with an alcohol, diluted, diluted with water and / or an organic solvent, to apply the reaction at a higher temperature to the powdered polymer.

157 /) 77 / //..'/ - .. // 7. , 77/7 .- / ·. 7 «· * ⁴ t

According to DE PA 4020780, the improved swelling ability of a superabsorbent polymer under pressure is achieved by heating the polymer powder with '0.1-5% by weight.

) ..// 77 alkylene carbonate, which is carried as required. 20 diluted with water and / or alcohol.

v.

Like DE OS 35 23. 617, as well as EP 04 50 924 AZ, the surface of the absorbent polymer is treated with a polyol which is optionally diluted with water and / or an organic solvent. The significance of the treatment medium / dilution with water and / or organic solvent ..)) is thoroughly investigated in this publication. . ..The dilution / treatment agent capable of reacting with the carboxylic groups of the polymer, with only 30 water, presents enormous technological difficulties. When in contact with water or an aqueous solution in powder form, the water-swellable polymer is sintered in such a way that homogeneous processing agents / distribution on the particle surface are rendered impossible.If we do not dispense with water-swellable powder polymer to mix with a compound. carboxyl groups of the polymer,

i / '· - // 5 ^; in order to support the diffusion of the treatment agent into a solid 4 _Λ · 4 · \ · ../ ^^ being forced to make water more inert using excess treatment agent or unreacted organic solvent. Making more inert with an organic solvent means using liquids that do not / do not swell the polymer; this means that t or combing will not occur during the mixing process with the powdered polymer.

One skilled in the art will have difficulty in blending a small amount of liquid into a powder material homogeneously, particularly when it is necessary to coat each individual grain uniformly.

High dilution of the treatment agent with an organic solvent would positively influence the distribution of the treatment agent on the surface of the powdered polymer, but / using / greater than 1 wt% liquids results in a wet polymer powder that clogs the transport systems continuously.

By increasing the amount of the treatment agent *, the distribution of more than 1% by weight is improved, but a moist, sticky powder is obtained. If, in order to accelerate the diffusion of the treatment agent into the grain of the polymer, more water is added to the treatment agent than is required to make about 50% of the solution prior to the mixing process, the powdered polymer will sinter. In EP 04 50 923 A2, a continuous water-swellable polymer blend with processing agent solution in a special Synthetic-coated blender method prevents wet polymer / powder from sticking to the blender, reducing the cost of blending, but does not improve the behavior of the blended product.

According to the process of EP-PS OO 83022, the water-containing polymeric particle is subjected to further treatment. .in organic solvent .. After mechanical separation of the polymer sequence. - drying, during which

- Inevitably - -Condensed from water and an organic solvent, such as alcohol, hydrocarbon, chlorinated hydrocarbon or ketone. After all, the resulting condensate must be recycled so that the solvent components are not released into the environment through the blown air or through the wastewater.

-The following conditions are required for the coating of the water-swellable polymer in powder form, which is to be delivered in reaction to the surface layer of each individual particle;

The amount of processing agent should be sufficient to achieve an even coating of the polymer powder.

The amount of water that serves as a vehicle for distribution and as a carrier for the treatment medium to the polymer surface is limited, otherwise irreversible sintering of the polymer particles occurs. '

The total amount of treatment agent, water and, if necessary, organic solvent is limited, otherwise wet, impervious mixtures will be formed.

If the process of mixing a water-swellable polymer with a treatment agent is viewed separately from the general production process, the use of an organic solvent in combination with a treatment agent _t seems to be most appropriate. In this case, the distribution of the treatment agent and limited amounts of water on the polymer powder is assured. So too

larger treatments; the use of amounts results in a good distribution on the polymer / - also in the presence of water - where the treatment agent can take over the role of an organic solvent / t. y. interferes with the · sintering of the powdered polymer. However, according to EP .04 50 923 • A2, excessive use of the curing agent can lead to a significant decrease in the / swelling capacity of the polymer. . · / /·/.'/

However, also under optimum conditions / in the form of a powder, water-swellable polymer and, if necessary, dilution. means for mixing ^r '• process; The reaction at a higher temperature should then be considered. If the properties of the swabberabsorbudjahchid / polymer are improved. can be achieved by additional esterification and / or / amidation of polymer / carboxyl groups,>'it'B / past. for reactions // B reaction times B · temperatures B> 150 ° C are required. In this temp tour the party is near the van. water containing 8-15% w / w of the initial polymer and solvent evaporation are also significant amounts of the treatment medium that are / are to be // removed from the reagent or dryer. in order to prevent condensation in the reactor./Target / secondary vapor. transport, if necessary, is accomplished by the use of preheated scrubbing gases, / because condensing water vapor can spin / powder polymer polymer, and coalescing agent can cause / powder polymer sintering and fading.

Water vapor, Steam remover / Treatment B, Oxygenates, Residual monomers and others

B B · The volatile products of the reaction and the organic solvents from the B effluent / gas are very difficult to remove. y. forcibly enters air or / waste water.

^8th It is an object of the present invention to provide superabsorbents having a combination of properties such as high retention capacity, high gel strength and high pressure absorption capacity, which can be

- made without the use of an organic solvent and using a small amount of processing agent for further processing of the powdered polymer.

This objective is achieved by taking advantage of the essential features of point 1 10 '. Y Remarkably, when using - phosphoric acid as a diluent for the medium, with

The Y on which the surface of the absorber to be treated is treated can provide superabsorbent Y with the desired properties. combination, significantly reducing processing agents 15. quantity. ·, / '/' //: Υ · _<: '' / '· / ΥΥ' / ';' Y / Yk / 5Y.g '.

Most preferably, phosphoric acid is used in amounts of up to 10 parts by weight (all parts below are parts by weight) of 100 parts by weight of polymer and using a concentration not exceeding 10% by weight. After using it

0.1% by weight of H ₃ PO ₄ , calculated with respect to the polymer powder, provides / superabsorbents according to the invention. . Y,

... '. to ··. Y *

According to the invention, the treatment means used are:

(a) 0.05 to 0.3 parts by weight of a compound which can react with at least two carboxylic carbon groups of the polymer in powder form and does not contain alkali metal salts

Y-forming groups, mainly polyols such as ethylene glycol, propanediol, polyethylene glycol, glycerol and alkyl carbonates such as ethyl carbonate, and / or

b) 0.05 to 1 part of a compound which is capable of reacting with at least two carboxylic groups of a polymer in the form of a powder and which additionally contains an acidic alkali metal salt moiety, e.g.

B

77 ...

polyhydroxycarboxylic acids? ///.like // / dimethylp.prppionic · // acid (= 2, '2-bis (hydroxymethyl j prdpioic acid). 7/7 /// 17 //./ :, 7 /.//// /// 4 //////////////

The treatment agent according to b) has the advantage that in reaction 7 with a powder polymer polymer.? //./ · /. _; /;-//.buckle & lashes ////because of the formation of salts in the surface layer of the polymer, its volatility is limited, 'y yy /.///y//^/(7/////////-/ /.

; / 7 / '/ 7 The water-absorbing polymerisate, which may be yy / y, is obtained by polymerization of 5599.9% by weight of monomers .. with acidic groups. e.g.

'Acrylic acid, methacrylic acid, 2-acrylamide p-215' methylpropanesulfonic acid or mixtures of these monomers; at least 25 mol% / acid groups are neutralized, e.g. such as sodium, potassium or ammonium salts.

Basically, the degree of hydration is at least '50 mol%. Particular preference is given to the polymerization of crosslinked acrylic or methacrylic acid, which is neutralized up to 50-80 mol%.

Of other monomeric water-absorbing hydrolysates. 0-40% by weight of acrylamide, methacrylamide, hydroxyethyl acrylate, dimethylaminoalkyl (meth) acrylate, dimethylaminopropylacrylamide or acrylamidopropyltrimethylammonium chloride can be used. More than 40% of these monomers impair the ability of the polymerizate to swell.

All compounds having at least two ethylenically unsaturated double bonds or one ethylenically unsaturated / double bond and a functional group capable of reacting with acidic groups or multiple functional groups capable of reacting with acidic groups may be used to form the spatial structure of the transverse bonds. Examples include: polyol acrylates and methacrylates such as butanediol acrylate;

- hexanediol dimethacrylate, polyglycolic acrylate, trimethyl isopropane acrylate or allyl acrylate, diallyl acrylamide ', triallylamine, diallyl ether, methylenebisacrylamide or N-methylolacrylamide. 10 * '· L.'

The water-soluble polymer in the water-absorbing polymer may be 0-30% by weight of partially or fully saponified polyvinyl alcohol, polyvinylpyrrolodone, starch or starch derivatives, polyglycols or polyacrylic acids. These polymers have a non-critical molecular weight while still soluble in water. Priority in Aquarius. soluble polymers are starch, polyvinyl alcohol or mixtures of these polymers. The preferred amount of such water-soluble polymers in the water-absorbing polymerizate is from 1 to 5% by weight, in particular. where the water-soluble polymers are starch and / or polyvinyl alcohol. Water-soluble polymers. may be graft copolymers having acidic groups.

In addition to the polymerisates obtained by the spatial polymerisation of partially neutralized acrylic acid, particularly those containing additional amounts of starch or polyvinyl alcohol grafted copolymers are used.

There are no specific limitations on the particle shape of the absorber polymer used. The polymer may be in the form of spheres which are obtained by inversion suspension polymerization or in the form of irregular particles which result from the drying and production of a powder of the gel obtained by polymerization.

3079Β: '' in solution 11. · Typically, the particle size is between 20 and '2.0O0 µm, with particles of 50 and 850 μιη being preferred. .

The heat treatment after coating is carried out

150-250 ° C, preferably 170-200 ° C. temperature. It depends on the retention time and the type of treatment medium. ' At 150 ° C, the heat treatment has to be carried out for many hours, while at 250 ° C several minutes. - e.g.

0.5 to 5 minutes5 is sufficient to obtain the desired properties. Heat treatment may be carried out in conventional dryers and furnaces; examples include a rotary kiln, a rotary kiln, a plate dryer and an infrared dryer.

The polymers ^f according to the invention have a more developed spatial structure and a reduced degree of neutralization near the surface.

'20' 3 'M / 3' y / t: //-3//7(-3.(5 5 /(-.7-^/7,/(/.,^(.//3 (/ /..(7(,,(,/',:,;3·ρ;//>./3£

The inventors / polymers can be produced by a continuous and intermittent process. The superabsorbents of the invention can be used in a wide range of applications. When used on women's tampons and diapers or wound dressing, they have the ability to quickly absorb large amounts of menstrual blood, urine or other body fluids.

Compared to the original products, the ability to absorb and the rate of absorption at the same time under a compressive load were greatly improved. Because the superabsorbents of the invention retain ·· absorbed fluids and under pressure, they are particularly suitable for use. They prefer using. Higher concentrations - 'compared to hydrophilic fibrous downs - that have been possible up to now and exhibit excellent absorption properties (·: χχχΧ / Χΐχ'.Λ //. Χ12ΧΧ in structures containing 98-20% by weight hydrophilic of fibers and 2 to 80% by weight of adsorber resin.

According to the invention, further processed polymers in the 5 'absorbent articles are used for a variety of applications, e.g. by mixing with paper, down, or synthetic fibers; or by partitioning the substrate from paper, down, or nonwovens, or by reshaping the material 10 into a web.

The superabsorbent waits obtained by the described process exhibit a significant improvement in the absorption of the fluid under pressure in terms of speed and overall capacity, while at the same time having a "high gel strength and high retention", achieving extremely high initial fluid absorption times, yes, 'in 15 minutes, 80%' of the total capacity. Absorption after

The X pressure given in DE PS 40 20 780 and EP A 03 39 461 as absorption under load (AVL) strongly depends on the size of the load. The polymers described therein have an absorption capacity of 0.9% sodium chloride solution at 20 g / cm ² (= 0.28 psi = 19.600 dyn / cm ² ) equal to 26 to 34 g / g. The polymers described in EP A 03 39 461 have an absorption capacity of 0.53 psi at 13 g / g and a load of 0.85 psi at 8 g / g; that is, the treated polymers at a load of 0.85 psi absorb only the amount of liquid that, according to DE PS 40 20 780, is absorbed by the additionally untreated, water-swellable polymer under a higher load.

0.9% strength of absorbent solution of the polymer according to the invention at a load of 40 ^; . g / cm ² ·,. at least 15 g / g, most more than

18 g / g. At a load of 60 g / cm ² , the absorbed liquid is more than 12 g / g, preferably more than 15 g / g. This is unexpected because according to DE PA 40 20 780, y; ./7.--7.77/..+,13 ../ + / 7.

in order to increase the value of + 'AVL + (20 g / cm ² ), it is necessary to increase the amount of the post-treatment medium from 0.5' to 1.5% by weight. However, as a result of this measure, especially when water is used together to dissolve the alkylencarbonate, a wet non-pneumatic mixture is formed and excessive emissions occur during subsequent heat treatment.

Manufacturers of textile structures used to absorb body fluids / aim to reduce high volume fibers 7 and 7 to increase superabsorbent content. However, the textile structures must still be able to · retain under the load the particles that have swollen after liquid absorption. Because the fabric structure for absorbing body fluids is a high-porosity structure that can exert a soft, leakage gel under pressure, the challenge is to produce water-swellable polymers with high pressure resistance.

The polymers according to the invention exhibit not only increased absorption of 0.9% sodium chloride solution under pressure, but also high blood absorption capacity and faster blood distribution in the textile structure: under pressure. Therefore, polymers are especially; Suitable as absorbents in women's tampons as they have the ability to quickly absorb body fluids such as blood under weight. Blood absorption rate at the same time under pressure; load is significantly higher than that of known products.

Practice this simulation test, - //. for the determination of the suction properties of polymers under pressure, it can be shown that superabsorbents - also polymers described in EP A 03 39 461 - have a high suction / power at a load of 20 g / cm ² and a load of 60 g / cm ² , swell to a considerable extent. The following test 7 / shows swelling polymers having the same retention and absorption at higher load; may vary according to ijali. 777. // / sampling / water injection at 2 0 / g / cm ² , ability at suction

Accordance with the invention _r polymers under a load of 20 g / cm ² may -sugerti textile structure like the same amount of liquid as in the unloaded state .-- This means that for example. the baby's body diaper down layer is more secure and dries faster, ”and as a result, moisture is isolated from the skin.

'i -V' fr is distinguished

The dynamic increase in pressure in which the water in the ocean is squeezed after 1 minute of immersion is called swelling pressure. / During swelling, this pressure increases until an equilibrium is reached between the electrostatic forces in the polymer and the external mechanical forces. 7 7

The polymers of the invention exhibit up to four times the swelling pressure compared to commercially available superabsorbents.

25 'Preference is given to water-swellable polymers with a swelling pressure of 400 g and particularly preferred to swelling polymers with a swelling pressure of more than 600 g at a swelling area of 4.91 cm ² .

The polymers of the invention are tested as follows:

Test methods

For the characterization of water-absorbing polymerizates, 35 retention (TB) and 7 under pressure (AUL) of NaCl solution were measured, as well as the absorption capacity and absorption rate of defibrated sheep blood.

'15,

(a) Retention was measured by the tea bag method and reported as the average of three measurements. Approximately 200 mg of polymerizate are immersed in a tea bag and immersed in 0.9% NaCl solution for 20 minutes. The ora bag is then centrifuged in a centrifuge (23 cm diameter, i.400 rpm) for 5 minutes and weighed. The blank was tested on a tea bag without water-absorbing polymer.

+, 'G' + '/' 7 '/ + - G,, weight after test - blank test

Retention = ...................- - .: '- · - weight before test' v / ' ⁷ ' /: +. ' / U ⁷ /

b) The pressure absorption of 0.9% NaCl (load 20, 40, 60 g / cm ² ) was determined according to EP 03 39 461, p.

7,

.20 A weighed quantity of superabsorbent is placed in a sieve-bottomed cylinder and the powder is pressed with a puncture of 20, 40 or 60 g / cm ² . The cylinder is then mounted on _: - Demand-AbsorbCncy-Tester (DAT), where the superabsorbent absorbs 0.9% of the substance for 1 hour,

NaCl solution.

(g) For determination of the absorption capacity, approximately 200 'mg of polymer is immersed in a tea bag and immersed in defibrated sheep blood for 60 minutes and then weighed.

The calculations shall be carried out as in (a).

d) On 6 cm x 20 cellulose fabric (48.8 g / m2) · 1 g of polymer evenly spread, fabric

- covered with a cloth of the same size and pressed at 100 ° C at a load of 400 g / cm ² .

The test strip is placed between. two glass + panels with the top panel in the middle

hole. A 5.5 cm long and 2.2 cm internal diameter tube is inserted into the hole. A weight shall be applied to the top plate such that the test strip is loaded at 30 g / cm ² . Hose pump 5 cm? defibrinated. 20 ° C. the sheep's blood is poured into the tube within 30 seconds and the drinking time is determined,

e) The swelling pressure Q is determined using Stevens L.F.R.A. Texture Analyzer, C. Stevens and Son Ltd, 'Laboratory Di Vision, /. Sf 7 / 'Albąns // AL 1 lEx Hertfordshire, 7 <-. · 7 \ England ^ 70 // 7 /

The device-dependent cylindrical measuring / body is 3.5 cm high and 2.5 cm in diameter. In this way, the circumference of the cylinder is 4.91 cm.

Weigh, weigh and dispense 20 g to 50 mesh of G0 & O g super-bent fraction into a suitable measuring cylinder of 2.7 cm diameter and fill with 10 / έ, 0.9% NaCl solution; The technician then moves the measuring cylinder until the distance between the lower end of the measuring body cylinder and the specimen in the measuring cylinder is 12 mm. As the gel expands, the measuring cylinder is pressed upward into a two-way force measuring cell; device.

gives data in grams- ·.

The following examples further illustrate the invention:

'.Examples '

A) Polymer A Blend and Treatments ·

A polymerization solution thus obtained powder 35 trimetilolpropantriakrilato aid bonded to transverse 0/7 'connectors, polyacrylic acid with a 70 mole% / were in the beginning e • .peutraLįziK> that / ⁱ / ikii: / ^ iBatri / Hruskoj.. after milling, particles of 90 to 850 gm were seeded ({polymer A).

TB (retention): 36 g / g water content: 10.4%.

The polymer is poured continuously at 1000 kg / h into a blender mixer (750 rpm) and mixed with a treatment agent. Thereafter, the mixture enters the transport system and is transported to a collection tank. The essential properties and, at the same time, the behavior of the solid-liquid mixture during transport and time are evaluated. '. ·· {' (B '.. · .0 Table

Examples Treatment tool. Solid-liquid mixture b ^; /%b./b (<% · '; <' ( ΒΒ; '% 0 Appearance Behavior B <( 1 Comparison 0.5 EC 0.5H ₂ O '· .step B, loose Comparison 2 1.0 EC i, oh ₂ o 0 - '' -0 .. wet sintered 3 Comparison 0.25EC 0.25H ₂ O 'B-'B /' G dry . . B / loose 4 Comparison 0.5 GI O, 5H ₂ O ', -' / - <. '000 wet. <-. /.dirty. B-Β. 5 Comparison 0 / 25G1 0.25H ₂ O l, 0Et '' wet 'bb loose Example 1 0.1EC i, oh ₃ after ₄ dry H loose Example 2 0, lGl 0, 6H ₃ PO ₄ 0, 3H, 0 - dry (0B loose

EC: ethylene carbonate

GI: Glycerin

H ₃ PO ₄ : 85% phosphoric acid

Et: ethanol

Comparisons -From comparisons 4 to 3 corresponds to DE-PS 40/20 78,

- DE-OS-35 23 617.

B) Heating of blends from polymer A and processing agents

According to A) obtained in bulk, i.e.//y. suitable mixes are dosed at 90 kg / h into a 180 ° C-steam / dehumidifier: Drying capacity is 40 1. Secondary / steam flushing air volume is / 50 m3 / h.

The data in the table below refer to the resulting powdered polymers as well as the amount of organic matter in the waste gas, referred to as Organic Carbon (TOC).

table

Example -. ^: '//' - / Mixture / -: into TB AUL 20 g / cm ² TOC sample) [g / g] to [g / g]

6 Comparison 1 Comparison ) / 7) / 32) - /. /, 7 // .///-,30.)7))/ /)711.5)):-- ¹ 7: Comparison ' '3 Comparison ) 77)) 33 / -7 .7 // 7) 2477 // 7 / 77 / 4-4 // 8 Comparison // 5 Comparison 7712/7) ) 7 - /) // 77 317)) / -: /) 7) .-- 320 *)  Example 3 Example 1 7732/77 :) ..: 7 / Zai30 '- // 7) ///,. 7/14 Example 4 Example 2 ) //) / 7/10:) /).) - / .7)) - 74 / -. -

*) part of the ethanol is evaporated / during mixing and transport ./:/ / (feeding) '/ 7, / j //) /. 3 '

C) Preparation of Mixture from / Polymer B / Treatment // // // //;

.? /'.'/ 7 · /// 7.77χ1π ^ -7 .///- 7 / - / ζ // 77 // 7’-7 //) ^: ·

Polymer obtained by polymerization of / 30% aqueous acrylic acid. which: was neutralized to 60

7: Molar% sodium Z in 0.28% w / w trialilamine and 3.5% w / w polyvinyl alcohol, dried to 160 ° C / hot air, milled and seeded from / 120 g / 50 '/ particles (polymer B). '//.). --- 7 ..////:/

TB; 37 g / g water content 10.5%; LA11.8%.

7 7 '//' 19 // '' ///// ''

Polymer B, like polymer A, is mixed with ± 2% by weight of a solution of 0.2 parts of dimethylolpropionic acid and 1 part of 85% phosphoric acid at 40 ° C and placed in a hopper.

D) Heating the mixture according to C)

The bulk mixture obtained in (C) is fed into the dryer of the pneumatic conveying system into a dryer having rotary steam-heated, disc-shaped stirring elements at 184 ° C and then cooled in a fluidized bed. Product data and TOC values are shown in Table 3.

Table 3

An example Skippable forces : / tb / | // [g / ^ AVL / g / g / at load / download Ιθ ||| IlStJ g / cm ² i | 4o || g / cm ² 60 g / cm ² | // | / ® / J / BlKSSS / ® /: · ®kS® // ii / ® S® / ® come in '4.5 6.7 | to® // | ® || // ®3l // §is> // _; | · /// // 33®: SS® / • ®S® sus 5.0 - ®l® / 7 / | ®3 ii®® '/'?!; /: ® / ® /: SSs® iSS® INSI® 23.5 - 4.2 '

*} LA: soluble parts as defined in EP A 02 05 674

Table 4

Determination of blood absorption capacity and velocity

An example Polymer Adsorption «Bcj / gj / y Adsorption rate at 30 g / cm ² , [min] // ®1® / ® / ®3®3® from Example 3 ² S®37, S // '/? / .// S | S || S ||||||| 9 Comparison EAU0R S © *) ΈΑΜ 44 ' / 3 / ®3 / ·: 3 / · /: 1 / 3Ο '// ² :: //' // · ^Ί / 3 '/.

*) Manufacturer: Chemical plant in Stoękhaūsen, Krefeld

Determination of Suction Properties of Polymers from Matrix.

. 6 cm. in diameter and. A 2 g4 round fluff pillow in a Petri dish is impregnated with various volumes of 0.9% NaCl solution. 0.20 g of polymer weighed is introduced into a 28.75 'mm plexiglas cylinder of inner diameter (36 mm mesh size) on the underside.

'and fastened with a 25 mm diameter 106 g bag. Cylinder ^. the group (cylinder, polymer and poisson) is weighed (A) and placed in the middle of the moistened cushion. One hour later, the cylinder group is weighed again (B).

. .. .g _;; .

Suction properties = ————————————————— g / g table

table

Determination of swelling pressure

Time [min]. 2 3 '· ³ 10th 15th Polymer from Example 7 200 ' 410 520 820 825 FAVOR SAB 800 ¹¹ 195 · 240 250 260 260

1) Manufacturer: Chemical plant Stodkhausen GmbH, Krefeld

Claims (7)

DEFINITION OF INVENTION 1. In powder form. polymer to absorb aqueous fluids and blood under pressure; and 5 having a spatial structure consisting of (a) 55% to 99,9% by weight of polymerised unsaturated polymers which contain acid groups of at least 25 mol%, 10 ' b) 0-40. % by weight of polymerised unsaturated monomers capable of copolymerization with (a), n) 0.1-5% by weight of the means comprising the transverse 15 connectors, d) 0-30% by weight of a water soluble polymer, wherein the amounts of a) to d) are calculated on the anhydrous basis 20 polymers, comprising mixing 100 parts by weight of a * polymer with vandal solution containing up to 10 parts of at least 10% phosphorus, acid and 25 (a) with from 0, 05 to 0.3 parts of a compound which can react with at least two carboxylic groups and has no alkali metal salt moiety, and / or B) 0.05 to 1 part of a compound which is capable of reacting with at least two carboxylic groups and has a alkali metal salt-forming group and is heated to 150-250 ° C. 35 2, A polymer according to claim 1, characterized in that it has? 23; (a) a retention of 27 to 34 g of 0.9% sodium chloride solution per gram of polymer, (h) weighing more than 15 g and more than 18 g / m. Absorption of 0,9% edible salt per gram of polymer / at a pressure of 40 g / cm ² , (c) Absorbing more than 12 g, but not more than 15 g, per gram of edible salt 7 / 0.9% 10 polymers at 60 g / cm ² , (d) a swelling pressure of more than 400 g and more than 600 g. 15th 3. Polymer _{: as} claimed in claims 1-2. a nt is that it consists of // acrylic acid, -. methacrylic; acid and / or 2-acrylamino-2-methylpropyl, sulfonic acid, as an acidic monomer. 20; '' '77' · .- / 7 ... / lli / pen '/. 4. Polymer according to claims 1-3, characterized distinguished nt i S ³ in that the acidic groups containing moromerąi is to neutralize at least iki50 mole%. 7th 5. A polymer according to claims 4, characterized in that it consists of up to 50-80 mol% of neutralized acrylic acid as the only acidic monomer. 6 / Polyester according to claims 1-5, characterized in that from 1 to 5% by weight of water-soluble polymers 7 'are used. Polymer according to claims 1-6, characterized in that starch and / or polyvinyl alcohol is used as water-soluble polymers. ... '. ^? 155 /.// //-//5.55////./,///-. 24 / ,,. 5 /.- / 5 0 /./ 5. / 8. A process for the preparation of a powdered polymer for absorption of aqueous fluids and blood ⁷ 5. (a) 55% to 99,9% by weight of polymerised unsaturated polymers which contain acid groups of at least 25 mol%, b) 0-40% by weight of polymerized unsaturated monomers which can be copolymerized with a), c) 0.1-5% by weight. means forming transverse connections, 15 d) 0-30% by weight water-soluble polymer ku'r amounts of a) -d) are calculated on anhydrous polymers, characterized by ^one duck that is mixed to 100 parts of particulate polymer with a solution containing up to 10 parts of at least 10 20% phosphoric acid and (a) 0.05 to 0.3 parts of a compound which can react with at least two carboxylic groups and has no alkali metal salt moiety; 25 and / or 55 /, -'Ή '·' / '-.; ./ ·'<555 / ... t /; ·; ' · // '/ · ;. · '// / 5 -5. '' .5. / · '': 5 5 _v (b) 0.05 to 1 part of a compound which can react with at least two carboxylic groups and has a alkali metal salt-forming group; 30 and heat to 150-250 ° C. 9. The use of a polymer in textiles for absorbing body fluids under an increased load, in which the polymer has: 35 ' 5 a) retention of 27 to 34 g of 0.9% sodium chloride / tif retention per gram of polymer, b) Absorbing more than i'5 g, mostly greater than IP d, '0.9% edible salt per gram of polymerosate at 40 g / cm ² , • 5 c) More than 12 g, mainly greater than Absorption of 15 g, 0.9% edible salt per gram of polymer at 60 g / cm ² , ' (d) weighing more than 400 g but not more than 600 g, 10 swelling pressure. Use of a polymer according to claim 9 in articles comprising hydrophilic fibers and 2-80% Thickness polymer based on total weight.